AU2020347901A1 - Method for the heterogeneous catalysis using a ferromagnetic material heated by magnetic induction and catalyst support used for said method - Google Patents

Method for the heterogeneous catalysis using a ferromagnetic material heated by magnetic induction and catalyst support used for said method Download PDF

Info

Publication number
AU2020347901A1
AU2020347901A1 AU2020347901A AU2020347901A AU2020347901A1 AU 2020347901 A1 AU2020347901 A1 AU 2020347901A1 AU 2020347901 A AU2020347901 A AU 2020347901A AU 2020347901 A AU2020347901 A AU 2020347901A AU 2020347901 A1 AU2020347901 A1 AU 2020347901A1
Authority
AU
Australia
Prior art keywords
ferromagnetic material
iron
catalyst
wires
reactor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
AU2020347901A
Inventor
Juan Manuel ASENSIO REVERT
Julian Carrey
Bruno Chaudret
Stéphane FAURE
Sumeet KALE
Pauline KERROUX
Julien Marbaix
Nicolas Mille
Aikaterini Soulantika
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Institut National des Sciences Appliquees de Toulouse
Original Assignee
Centre National de la Recherche Scientifique CNRS
Institut National des Sciences Appliquees de Toulouse
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Centre National de la Recherche Scientifique CNRS, Institut National des Sciences Appliquees de Toulouse filed Critical Centre National de la Recherche Scientifique CNRS
Publication of AU2020347901A1 publication Critical patent/AU2020347901A1/en
Pending legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/755Nickel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12Silica and alumina
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/745Iron
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33Electric or magnetic properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/40Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/50Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/50Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58Fabrics or filaments
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/12Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon dioxide with hydrogen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/50Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00433Controlling the temperature using electromagnetic heating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/001Controlling catalytic processes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/10Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74Iron group metals
    • C07C2523/745Iron
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74Iron group metals
    • C07C2523/755Nickel
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/83Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with rare earths or actinides

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a method for the heterogeneous catalysis of a reaction for the hydrogenation of a carbon oxide in the gaseous state, such as a methanation reaction, using, in a reactor (1), carbon dioxide and gaseous dihydrogen and at least one solid catalytic compound capable of catalyzing said reaction in a given temperature range T, comprising contacting said gaseous reactant and said catalytic compound in the presence of a heating agent, and heating the heating agent to a temperature within said temperature range T. The method is characterized in that the heating agent comprises a ferromagnetic material in the form of micrometric powder and/or wires, said ferromagnetic material being heated by magnetic induction by means of a field inductor, such as a coil (2) external to the reactor (1). According to one embodiment, the catalyst support for implementing said method comprises a ferromagnetic material in the form of wires of micrometric diameters, on the surface of which metal catalyst particles are deposited.

Description

Description Title of the invention: Method for the heterogeneous catalysis using a ferromagnetic material heated by magnetic induction and catalyst support used for said method
[0001] FIELD OF THE INVENTION
[0002] The present invention relates to the field of heterogeneous catalysis, notably a gas-solid heterogeneous catalysis process comprising the contacting of at least one gaseous reactant with a catalytic solid compound positioned on a support. The present invention also relates to the support for said catalyst.
[0003] Very many processes require heterogeneous catalysis. These catalysis processes require a step of heating, sometimes at high temperature, for the implementation of the reaction, and are therefore expensive and highly energy consuming. Research has therefore focused on more economical solutions and notably on reactions that are less energy intensive.
[0004] PRIOR ART
[0005] Among these solutions, international application WO 2014/162099 has proposed a heterogeneous catalysis process in which the heating is carried out by magnetic induction in order to reach the temperature necessary for the reaction. More particularly in this process, the reactant is contacted with a catalytic composition which comprises a ferromagnetic nanoparticulate component, the surface of which consists at least partially of a compound that is a catalyst for said reaction, said nanoparticulate component being heated by magnetic induction in order to reach the desired temperature range. This heating may be carried out by means of a field inductor external to the reactor. In this system, the nanoparticles are heated by their own magnetic moment, enabling the startup of the catalytic reaction. The heating is therefore initiated within the very heart of the reactor, rapidly with minimal energy input. This results in substantial savings.
[0006] However, the cost of these reactions still remains high, due in particular the cost of the catalytic particles in nanometric form and more particularly the magnetic nanoparticles. Moreover, these nanomaterials must, in general, be handled with caution.
[0007] Another problem linked to the use of nanoparticles is the modification of their heating properties due, on the one hand, to their tendency toward sintering during high-temperature reactions, and, on the other hand, to aging resulting from a change in the chemical order in said nanoparticles (modification of the structure and of the local chemical composition).
[0008]OBJECTIVES OF THE INVENTION
[0009] A first objective of the invention is therefore to overcome the aforementioned drawbacks by further reducing the cost of these heterogeneous catalysis reactions, while maintaining the reaction performance thereof.
[0010] Another objective of the invention is to propose a process that makes it possible to reduce the proportion of the components in the form of nanometric particles in the reactor.
[0011]Another objective of the invention is to propose a heterogeneous catalysis process that exhibits a maintenance of the heating properties and of the catalytic properties over very long periods of time, while being suitable for intermittent operation.
[0012] Another objective of the invention is to propose a process for catalysis of a gas-solid chemical reaction, more particularly of a hydrogenation reaction of a carbon oxide in the gaseous state, such as a methanation reaction.
[0013] DESCRIPTION OF THE INVENTION
[0014] In the search for new savings, the inventors discovered, surprisingly, that the heating agent may not necessarily be in nanometric form, but may be present in the reactor in the form of micrometric powder or of wires.
[0015] For this purpose, the present invention proposes a process for heterogeneous catalysis of a hydrogenation reaction of a carbon oxide in the gaseous state, such as a methanation reaction using, in a reactor, carbon dioxide and gaseous dihydrogen and at least one catalytic solid compound capable of catalyzing said reaction in a given temperature range T, comprising the contacting of said gaseous reactant and of said catalytic compound in the presence of a heating agent, and the heating of the heating agent to a temperature within said temperature range T, the process is characterized in that the heating agent comprises a ferromagnetic material in the form of micrometric powder composed of micrometric ferromagnetic particles having sizes of between 1 pm and 1000 pm and/or of wires based on iron or on an iron alloy, preferably having a wire diameter of between 10 micrometers and 1 millimeter, said ferromagnetic material being heated by magnetic induction by means of a field inductor external to the reactor, the magnetic field generated by the field inductor external to the reactor having an amplitude of between 1 mT and 80 mT and a frequency of between 30 kHz and 500 kHz. The results obtained with such a heating agent which is no longer nanometric, but of much greater size, are equivalent to those obtained in the process of WO 2014/162099 with a ferromagnetic nanoparticulate component.
[0016] According to a first embodiment of the invention, when it is present in powder form, the ferromagnetic material is advantageously composed of micrometric ferromagnetic particles having sizes of between 1 pm and 100 pm, preferably between 1 pm and 50 pm, more preferably between 1 pm and 10 pm.
[0017] With such micrometric ferromagnetic particles, which admittedly sometimes have a tendency toward agglomeration, no sintering is observed and the effectiveness of the heating is thus maintained.
[0018] As regards the catalytic compound used in the process according to the invention, said catalytic compound comprises a catalyst for the heterogeneous catalysis reaction that is in the form of metallic particles positioned on a support.
[0019] Said metallic catalyst particles are advantageously chosen from manganese, iron, nickel, cobalt, copper, zinc, ruthenium, rhodium, palladium, iridium, platinum, tin, or an alloy comprising one or more of these metals.
[0020] Said metallic catalyst particles are positioned at the surface of an oxide forming a support for the catalyst, such as an oxide of at least one of the following elements: silicon, cerium, aluminum, titanium or zirconium, (for example A1203, SiO2 , TiO2, ZrO2, CeO2) constituting a catalyst-oxide assembly that is in the form of a powder of micrometric or nanometric size which is mixed with the ferromagnetic material in the form of micrometric powder. The mixing of these powders (catalyst-oxide assembly with the microparticulate ferromagnetic material) thus creates intimate contact between the heating agent and the catalyst, making it possible to rapidly start the catalysis reaction at the surface of the catalyst.
[0021] According to a second embodiment of the invention, the support for the catalyst is said ferromagnetic material that is in the form of wires.
[0022] Advantageously, the ferromagnetic material that is in the form of wires, which are supports for the catalyst, may comprise, or predominantly consist of, steel wool, containing wires based on iron or on an iron alloy, preferably having a wire diameter of between 20 pm and 500 pm, more preferably between 50 pm and 200 pm.
[0023] Indeed, quite surprisingly, steel wool, a cheap and readily available material that can be purchased in home improvement stores, has proved to be an excellent heating agent. More particularly, very fine (superfine) steel wool, having a wire diameter of less than a millimeter, is both a good catalyst support and effective for enabling the heating of said catalyst by magnetic induction.
[0024] This material is very easy to use and has a very long service life. Furthermore, it is easily recyclable and is non-polluting.
[0025] The process according to the invention is advantageously a hydrocarbon synthesis reaction, more particularly the heterogeneous catalysis reaction is.
[0026] The heterogeneous catalysis process according to the invention, hydrogenation reaction of a carbon oxide in the gaseous state, such as a methanation reaction starting from carbon dioxide and dihydrogen, may in particular be carried out with a magnetic field generated by the field inductor external to the reactor having an amplitude of between 1 mT and 50 mT and a frequency of between 50 kHz and 400 kHz, preferably between 100 kHz and 300 kHz.
[0027] The present invention also relates to a catalyst support for the implementation of the heterogeneous catalysis process described above, characterized in that it comprises a ferromagnetic material in the form of wires of micrometric diameters, deposited at the surface of which are metallic catalyst particles.
[0028] Advantageously, the ferromagnetic material is based on iron, or on an iron alloy, preferably comprising at least 50 wt% iron, more preferably at least 80 wt% iron.
[0029] This ferromagnetic material may in particular be composed of superfine steel wool, comprising an entanglement of wires composed of at least 90 wt% iron, and of which the diameter of the wires is between 10 pm and 1 mm, preferably between 20 pm and 500 pm, more preferably between 50 pm and 200 pm.
Brief description of the drawings
[0030] The invention will be clearly understood on reading the following description of non-limiting exemplary embodiments with reference to the appended drawings in which:
[0031] [Fig. 1A] is a simplified partial diagram of a reactor for the implementation of the gas-solid heterogeneous catalysis process according to the invention, under an upward gas flow, showing the positioning of the catalyst + heating agent assembly in the part of the tubular reactor encircled by the external magnetic field inductor,
[0032] [Fig. 1B] is a simplified partial diagram of a reactor for the implementation of the gas-solid heterogeneous catalysis process according to the invention, under a downward gas flow, showing the positioning of the catalyst + heating agent assembly in the part of the tubular reactor encircled by the external magnetic field inductor,
[0033] [Fig. 2] is a graph comparing the performance of various heating agents according to the invention, carried out under argon at 100 kHz (specific absorption rate, SAR, corresponding to the amount of energy absorbed per unit mass, expressed in watts per gram of material, as a function of the alternating magnetic field intensity applied, expressed in mT): iron powder having microparticles with a size of the order of 3-5 pm, fine steel wool (wire diameter of greater than 1 mm) and superfine steel wool (wire diameter of less than 1 mm, of the order of 100 pm),
[0034] [Fig. 3] is a graph presenting results of a methanation process according to the invention using iron powder as heating agent and an Ni on SiRAIOx@ ((silicon aluminum oxide from SESAL) catalyst,
[0035] [Fig. 4] is a histogram showing the conversion rates (in %) of C02 and of CH4 and also the selectivity as a function of time and temperature for a methanation reaction in downward flow in the presence of a mixture of iron powder and Ni/CeO2,
[0036] [Fig. 5] is a histogram showing the conversion rates (in %) of C02 and of CH4 and also the selectivity as a function of time and temperature for a methanation reaction in downward flow in the presence of a mixture of steel wool and Ni/CeO2,
[0037] [Fig. 6] is a histogram showing the conversion rates (in %) of C02 and of CH4 and also the selectivity as a function of time and temperature for a methanation reaction in downward flow in the presence of nickel on steel wool,
[0038] [Fig. 7] is a graph comparing the energy efficiency (expressed in %) as a function of temperature for the three types of catalyst beds (catalyst + heating agent) tested in the examples presented in figures 4, 5 and 6.
[0039] EXAMPLES
[0040] Example 1: Preparation of the catalyst
[0041] Preparation of the catalyst on cerium oxide support Nickel at 10 wt% on cerium oxide (abbreviated to Ni(10 wt%)/CeO2) is prepared by decomposition of Ni(COD)2 in the presence of CeO2 in mesitylene.
[0042] According to a conventional preparation process, 1560 mg of Ni(COD)2 are dissolved in 20 mL of mesitylene then 3 g of CeO2 are added. The mixture obtained is heated at 1500 C under an argon atmosphere for 1 hour with vigorous stirring. This mixture, initially milky white, is black at the end of the reaction. After decantation, the translucent supernatant is removed and the particles obtained are washed three times with 10 mL of toluene. The toluene is then removed under vacuum, making it possible to obtain a thick powder of Ni0 wt%/CeO2 (3.5 g) which is collected and stored in a glove box. Analysis by inductively coupled plasma mass spectrometry (ICP-MS) confirms the loading of 9 wt% of nickel (10% targeted) of the cerium oxide. Observation by transmission electron microscopy (TEM) and EDS analysis show the presence of small monodisperse particles of nickel (with a size of 2-4 nm).
[0043] Process for preparing Ni on SiRAIOx@ In a Fischer-Porter bottle and under an inert atmosphere, 0.261 g of Ni(COD)2 is dissolved in 20 mL of mesitylene and 0.500 g of SiRAIOx@ is added. The mixture is heated at 1500 C for one hour with stirring. After returning to ambient temperature, the powder is left to precipitate, then the supernatant is removed and the powder is washed three times with 10 mL of THF. The powder is then dried under vacuum and stored under an inert atmosphere.
[0044] Mixture of iron powder + Ni/CeO2 2 g of iron powder are mixed with 1 g of nickel catalyst deposited on cerium oxide prepared previously. Observation with a scanning electron microscope and also EDS mapping make it possible to visualize grains of iron powder having a size of the order of 3-5 pm and to confirm that the nickel is indeed present on the cerium oxide CeO2.
[0045] Example 2: Preparation of the catalyst on steel wool support
[0046] Superfine steel wool (Gerlon, purchased from Castorama). ICP-MS analysis of the superfine steel wool gives a composition of 94.7 wt% of iron. EDS mapping shows the presence of numerous impurities on the surface of the wool (mainly potassium, manganese, silicon). SEM observation makes it possible to determine the diameter of the wires of the superfine steel wool used, which is around 100 pm and has a rough and uneven surface.
[0047] The experimental protocol for depositing nickel metal on superfine steel wool (entanglement of wires of around 100 pm in diameter, containing 94.7 wt% of iron) is substantially the same as on CeO2. 1560 mg of Ni(COD)2 are dissolved in 100 mL of mesitylene in order to completely submerge the steel wool (3 g). After one hour under rapid stirring at 150 0C under argon, the mixture is placed in a glove box and the solution (of black color) is drained off. The steel wool has itself also turned black. The steel wool is then rinsed with toluene, and then dried under vacuum for 30 minutes and stored in a glove box. Observation by scanning electron microscopy (SEM) and energy-dispersive x-ray spectroscopy show the deposition of polydisperse particles of nickel (100 nm-1000 nm) on the surface of the wires of the steel wool.
[0048] ICP-MS analysis over three different zones shows different nickel loadings: 1.23%, 1.44% and 1.33% (weight percentages). These differences between these loadings are quite small, the surface of the wool appears homogeneous. Despite everything, the amount of nickel deposited is below the targeted percentage of 10 wt% of Ni.
[0049] Example 3: methanation reaction: measurements of conversion and calculation of the selectivity
[0050] The methanation reaction
[0051][Chem. 1]
CO 2 +4-H 2 -. CH+-2-H 20
[0052] which is a combination of
[0053] [Chem. 2]
-C02+-Hz-+->.CO+-Hz0.
[0054] and of
[0055] [Chem. 3]
C04-3-H---+-CH4+HzO
[0056] is carried out in a quartz fixed-bed tubular continuous reactor 1 (Avitec) (internal diameter: 1 cm with a height of catalyst bed 4, dependent on the heating element, of around 2 cm, resting on sintered glass 3) (cf. figure 1); the gaseous stream may be in upward flow 6 (Fig.1A) or in downward flow 7 (Fig.1B)). The coil 2 (from the company Five Celes) used is a solenoid with an internal diameter of 40 mm and a height of 40 mm that constitutes the external magnetic field inductor connected to a generator. Its resonance frequency is 300 kHz with a magnetic field varying between 10 and 60 mT. The coil 2 is water cooled.
[0057] The measurements of the conversion rates and selectivity as a function of the temperature are carried out with temperature servocontrol of the generator associated with the coil 2. For this purpose, a temperature probe 5 connected to the generator is submerged in the catalyst bed (heating agent + catalyst assembly). The generator sends a magnetic field in order to reach the fixed temperature and then only sends pulses to maintain this temperature. The reaction is carried out at atmospheric pressure and at a temperature that varies between 200 0C and 400 0C. The reactor 1 is supplied with H2 and C02, the flow rate of which is controlled by a flowmeter (Brooks flowmeter) and controlled by Lab View software. The proportions are the following: an overall constant flow rate of 25 mL/min comprises 20 mL/min of H2 and 5 mL/min of C02. The supplying is carried out at the top of the reactor, the water formed is condensed at the bottom of the reactor (without condenser) and is recovered in a round bottomed flask. The methane formed and the remaining gases (C02 and H2) and also the CO are sent to a gas chromatography column (Perkin Elmer, Clarus 580 GC column). The conversion of the C02, the selectivity of the CH4 and the yield of CO and of CH4 are calculated according to the following equations:
[0058] [Math. 2]
X(C2= 2 conversion (FC(CO) x A(CO) + FC(CH 4 ) x A(CH 4
) 15 X(C02) =CO2 co(FC(CO) x A(CO) + FC(CH4) x A(CH ) + A(C0 4 2
) Y(CO) =COyield (FC(CO) x A(CO) (FC(CO) x A(CO) + FC(CH 4 ) x A(CH 4 ) + A(C0 2
) Y(CH 4 )= CH 4 yield =FC(CH 4 ) x A(CH 4 )
(FC(CO) x A(CO) + FC(CH 4 ) x A(CH 4 ) + A(C0 2 )
S(CH 4 ) =CH 4 selectivity FC(CH 4 ) x A(CH 4 )
(FC(CO) x A(CO) + FC(CH 4 ) x A(CH 4 )
With FC(CO) = 1.61 and FC(CH 4 ) = 1.71.
[0059] FC is the response factor for each reactant according to reaction monitoring by gas chromatography, A is the area of the peak measured in chromatography.
[0060] Measurements of the energy efficiency: Energy efficiency measurements are carried out at the same time as the conversion and selectivity measurements of the methanation reaction. The electricity consumption data for the coil 2 are recovered by means of software developed in the laboratory. The energy efficiency is then calculated according to the following method
[0061] [Math. 2]
YCH4D,CH4- PCSCH4 D,, ..2 PCSz + Ebobi,
[0062] PCS (gross calorific value) represents the amount of energy released by the combustion of 1 mg of gas. The values given by the literature are PCSH2 = 141.9 MJ/kg and PCSH4= 55.5 MJ/kg, YCH4 being the CH4 yield of the reaction, Dmi being the mass flow rate of the product i, Ebobine corresponds to the energy consumed by the inductor in order to operate (namely, to generate the magnetic field and cool the system). The energy efficiency is expressed in % in figure 7.
[0063] Example 4: Comparison of various heating agents
[0064] Iron powder, fine steel wool and superfine steel wool were compared. The measurements of the specific absorption rate (SAR) (corresponding to the amount of energy absorbed per unit mass, expressed in watts per gram of material), as a function of the alternating magnetic field intensity applied, expressed in mT) were carried out at 100 kHz under argon. The results are grouped together in figure 2.
[0065] These results differ notably from those obtained in the recent publication by Kale et al., Iron carbide or iron carbide/cobaltnanoparticles for magnetically induced CO 2 hydrogenation over Ni/SiRAIOx catalysts, Catal. Sci. Technol., 2019, 9, 2601., which reports, for the FeC nanoparticles, SAR values of between 1100 and 2100 W/g at 100 kHz. Figure 2 shows that for a microparticulate ferromagnetic material such as iron powder or steel wool, these values are 10 to 20 times lower.
[0066] It might then be expected to have to provide the microparticulate iron powder and the steel wool with a higher field than for the nanoparticles. But the results from figure 3 show that this is not the case. For the iron carbide nanoparticles, it is necessary to provide a field of around 48 mT to achieve a yield close to 90%.
With the iron powder, after launching the reaction, a field of only 8 mT is necessary. The distinctive feature of the iron powder and of the steel wool lies in the eddy currents that come into play and lead to a reduction of the magnetic field for heating the material.
[0067] The micrometric iron powder and the micrometric steel wool therefore constitute advantageous ferromagnetic materials for in situ heating, by magnetic induction, of the reactors carrying out gas-solid catalytic reactions such as methanation reactions starting from carbon dioxide and dihydrogen, which is presented in the following examples.
[0068] Example 5: mixture of iron powders and of catalyst
[0069] The catalyst bed consists of nickel particles on cerium oxide: Ni : 0.09 g/ CeO2 : 0.91 g, mixed with 2 g of iron powder. The gas flow is downward, at a constant flow rate of 20 mL/min of H2 and 5 mL/min of C02.
[0070] The results of the conversion rates of C02 and of CH4 are presented in figure 4. This assembly of powders (iron powder + Ni/CeO2) makes it possible to obtain very satisfactory yields (Y(CH4)), reaching 100% at temperatures of 300-350C.
[0071] Example 6: mixture of steel wool and Ni/CeO2 catalyst
[0072] The catalyst bed consists of nickel particles deposited on cerium oxide: Ni: 0.09 g / CeO2: 0.91 g and of 0.35 g of (superfine) steel wool. The gas flow is downward, at a constant flow rate of 20 mL/min of H2 and 5 mL/min of C02.
[0073] The results of the conversion rates of C02 and of CH4 are presented in figure 5. This steel wool + Ni/CeO2 assembly also makes it possible to obtain very satisfactory yields (Y(CH4)), reaching 100% at temperatures of 300-3500 C.
[0074] Example 7: Ni catalyst deposited on steel wool
[0075] The catalyst bed consists of nickel particles: Ni: 0.03 g deposited on 2.27 g of (superfine) steel wool. The gas flow is downward, at a constant flow rate of 20 mL/min of H2 and 5 mL/min of C02.
[0076] The results of the conversion rates of C02 and of CH4 are presented in figure 6. The maximum yield (Y(CH4)) is 90% at 4000 C. This result is very encouraging, knowing that this system is simpler to implement.
[0077] Example 8: energy efficiency
[0078] The energy efficiency calculations of the preceding three examples (examples 5, 6 and 7) grouped together in figure 7 show that it is necessary to provide less energy to the steel wool system than to the iron powder system in order to reach the same temperature. This difference between powder and wool is observed particularly with the steel wool + Ni/CeO2 system. The energy efficiency of the steel wool + Ni is not as good since there is more wool to heat and therefore more energy to provide for a same amount of methane produced. In the example presented, it was necessary to introduce a large amount of steel wool, since very little nickel had been deposited thereon, in order to achieve an advantageous yield (90%).

Claims (13)

  1. Claims
    [Claim 1] A process for heterogeneous catalysis of a hydrogenation reaction of a carbon oxide in the gaseous state, such as a methanation reaction using, in a reactor (1), carbon dioxide and gaseous dihydrogen and at least one catalytic solid compound capable of catalyzing said reaction in a given temperature range T, comprising the contacting of said gaseous reactant and of said catalytic compound in the presence of a heating agent, and the heating of the heating agent to a temperature within said temperature range T, characterized in that the heating agent comprises a ferromagnetic material in the form of micrometric powder composed of micrometric ferromagnetic particles having sizes of between 1 pm and 1000 pm and/or of wires based on iron or on an iron alloy, preferably having a wire diameter of between 10 micrometers and 1 millimeter, said ferromagnetic material being heated by magnetic induction by means of a field inductor external to the reactor (1), the magnetic field generated by the field inductor external to the reactor having an amplitude of between 1 mT and 80 mT and a frequency of between 30 kHz and 500 kHz.
  2. [Claim 2] The process as claimed in claim 1, characterized in that the ferromagnetic material in powder form is composed of micrometric ferromagnetic particles having sizes of between 1 pm and 100 pm.
  3. [Claim 3] The process as claimed in in either of claims 1 and 2, characterized in that the ferromagnetic material in powder form is composed of ferromagnetic particles, having sizes of between 1 pm and 50 pm, preferably between 1 pm and 10 pm.
  4. [Claim 4] The process as claimed in one of claims 1 to 3, characterized in that the catalytic compound comprises a catalyst for the heterogeneous catalysis reaction that is in the form of metallic particles positioned on a support.
  5. [Claim 5] The process as claimed in claim 4, characterized in that said metallic catalyst particles are chosen from manganese, iron, nickel, cobalt, copper, zinc, ruthenium, rhodium, palladium, iridium, platinum, tin, or an alloy comprising one or more of these metals.
  6. [Claim 6] The process as claimed in either of claims 4 and 5, characterized in that the metallic catalyst particles are positioned at the surface of an oxide forming a support for the catalyst, such as an oxide of at least one of the following elements: silicon, cerium, aluminum, titanium or zirconium, constituting a catalyst-oxide assembly that is in the form of a powder which is mixed with the ferromagnetic material in powder form.
  7. [Claim 7] The process as claimed in one of claims 4 to 6, characterized in that the support for the catalyst is said ferromagnetic material that is in the form of wires.
  8. [Claim 8] The process as claimed in claim 7, characterized in that the ferromagnetic material that is in the form of wires, which are the supports for the catalyst, comprises steel wool, containing wires based on iron or on an iron alloy, preferably having a wire diameter of between 20 pm and 500 pm, preferably between 50 pm and 200 pm.
  9. [Claim 9] The process as claimed in any one of the preceding claims, characterized in that the magnetic field generated by the field inductor external to the reactor has an amplitude of between 1 mT and 50 mT.
  10. [Claim 10] The process as claimed in any one of the preceding claims, characterized in that the magnetic field generated by the field inductor external to the reactor has a frequency of between 50 kHz and 400 kHz, preferably between 100 kHz and 300 kHz.
  11. [Claim 11] A catalyst support for the implementation of the process as claimed in any one of claims 7 to 10, characterized in that it comprises a ferromagnetic material in the form of wires of micrometric diameters, deposited at the surface of which are metallic catalyst particles.
  12. [Claim 12] The support as claimed in claim 11, characterized in that the ferromagnetic material is based on iron or on an iron alloy, preferably comprising at least 50 wt% iron, more preferably at least 80 wt% iron.
  13. [Claim 13] The support as claimed in either of claims 11 and 12, characterized in that the ferromagnetic material is composed of superfine steel wool, comprising an entanglement of wires composed of at least 90 wt% iron, and of which the diameter of the wires is between 10 pm and 1 mm, preferably between 20 pm and 500 pm, more preferably between 50 pm and 200 pm.
AU2020347901A 2019-09-19 2020-09-18 Method for the heterogeneous catalysis using a ferromagnetic material heated by magnetic induction and catalyst support used for said method Pending AU2020347901A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR1910345A FR3100988B1 (en) 2019-09-19 2019-09-19 Heterogeneous catalysis process using a ferromagnetic material heated by magnetic induction and catalyst support used for said process
FR1910345 2019-09-19
PCT/FR2020/051625 WO2021053306A1 (en) 2019-09-19 2020-09-18 Method for the heterogeneous catalysis using a ferromagnetic material heated by magnetic induction and catalyst support used for said method

Publications (1)

Publication Number Publication Date
AU2020347901A1 true AU2020347901A1 (en) 2022-03-31

Family

ID=68654784

Family Applications (1)

Application Number Title Priority Date Filing Date
AU2020347901A Pending AU2020347901A1 (en) 2019-09-19 2020-09-18 Method for the heterogeneous catalysis using a ferromagnetic material heated by magnetic induction and catalyst support used for said method

Country Status (9)

Country Link
US (1) US20220370986A1 (en)
EP (1) EP4031281B1 (en)
JP (1) JP2022548714A (en)
CN (1) CN114630711A (en)
AU (1) AU2020347901A1 (en)
CA (1) CA3147973A1 (en)
ES (1) ES2956950T3 (en)
FR (1) FR3100988B1 (en)
WO (1) WO2021053306A1 (en)

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4359379A (en) * 1979-12-21 1982-11-16 Nippon Oil Company, Ltd. Process for fluid catalytic cracking of distillation residual oils
JPS5730786A (en) * 1980-07-31 1982-02-19 Nippon Oil Co Ltd Method for catalytic reaction of heavy petroleum oil
DE10350248A1 (en) * 2003-10-28 2005-06-16 Magnamedics Gmbh Thermosensitive, biocompatible polymer carriers with variable physical structure for therapy, diagnostics and analytics
WO2007135631A2 (en) * 2006-05-16 2007-11-29 Koninklijke Philips Electronics N.V. A soleplate
WO2011054738A1 (en) * 2009-11-06 2011-05-12 Basf Se Ferrous heterogeneous catalyst and method for producing olefins by converting carbon monoxide with hydrogen
SG11201407879SA (en) * 2012-05-29 2014-12-30 Univ Minnesota Biosynthetic pathways, recombinant cells, and methods
FR3003774B1 (en) 2013-04-02 2018-03-02 Institut National Des Sciences Appliquees De Toulouse CHEMICAL PROCESS CATALYSED BY FERROMAGNETIC NANOPARTICLES
PL407582A1 (en) * 2014-03-19 2015-09-28 Instytut Elektrotechniki Method for conducting chemical reaction using the powder catalyst
EP3237024A1 (en) * 2014-12-24 2017-11-01 Koninklijke Philips N.V. A new type of thermal catalytic oxidation material for air purification and apparatus therefore
CN108348881A (en) * 2015-10-28 2018-07-31 托普索公司 Ethylbenzene dehydrogenation is at styrene
FR3045412B1 (en) * 2015-12-18 2018-01-12 Institut National Des Sciences Appliquees De Toulouse IRON CARBIDE NANOPARTICLES, PROCESS FOR THEIR PREPARATION AND USE THEREOF FOR THE PRODUCTION OF HEAT
WO2017186615A1 (en) * 2016-04-26 2017-11-02 Haldor Topsøe A/S A process for the synthesis of nitriles
CN110095502B (en) * 2019-05-13 2021-10-22 合肥工业大学 Device for carrying out infrared road disease nondestructive testing by transmitting electromagnetism or microwaves

Also Published As

Publication number Publication date
FR3100988A1 (en) 2021-03-26
JP2022548714A (en) 2022-11-21
WO2021053306A1 (en) 2021-03-25
EP4031281B1 (en) 2023-06-21
CA3147973A1 (en) 2021-03-25
FR3100988B1 (en) 2023-03-10
EP4031281A1 (en) 2022-07-27
US20220370986A1 (en) 2022-11-24
ES2956950T3 (en) 2024-01-05
CN114630711A (en) 2022-06-14

Similar Documents

Publication Publication Date Title
CA2826734C (en) Fischer-tropsch catalysts
Xu et al. The promotional effect of surface Ru decoration on the catalytic performance of Co-based nanocatalysts for guaiacol hydrodeoxygenation
Jia et al. Crystal-plane effects of anatase TiO2 on the selective hydrogenation of crotonaldehyde over Ir/TiO2 catalysts
Macario et al. Nanostructured catalysts for dry-reforming of methane
Riani et al. Cobalt nanoparticles mechanically deposited on α‐Al2O3: a competitive catalyst for the production of hydrogen through ethanol steam reforming
Park et al. Synthesis of Co/SiO 2 hybrid nanocatalyst via twisted Co 3 Si 2 O 5 (OH) 4 nanosheets for high-temperature Fischer–Tropsch reaction
Gai et al. Recent advances in nanocatalysis research
Alshammari et al. Metal nanoparticles as emerging green catalysts
Liao et al. Benzene hydrogenation over oxide-modified MCM-41 supported ruthenium–lanthanum catalyst: The influence of zirconia crystal form and surface hydrophilicity
Fan et al. Synergistic catalysis of cluster and atomic copper induced by copper-silica interface in transfer-hydrogenation
Sun et al. CO 2 electrochemical reduction using single-atom catalysts. Preparation, characterization and anchoring strategies: a review
Gu et al. Mobility and versatility of the liquid bismuth promoter in the working iron catalysts for light olefin synthesis from syngas
André et al. Nickel carbide (Ni 3 C) nanoparticles for catalytic hydrogenation of model compounds in solvent
Ding et al. Revisiting the syngas conversion to olefins over Fe-Mn bimetallic catalysts: Insights from the proximity effects
Chernyak et al. Effect of cobalt weight content on the structure and catalytic properties of Co/CNT catalysts in the fischer–tropsch synthesis
US20220370986A1 (en) Method for the heterogeneous catalysis using a ferromagnetic material heated by magnetic induction and catalyst support used for said method
US20230241588A1 (en) Catalytic assembly comprising a micrometric ferromagnetic material and use of said assembly for heterogeneous catalysis reactions
Zhang et al. Theoretical and experimental insights into CO2 formation on Co2C catalysts in syngas conversion to value-added chemicals
Pei et al. Preparation of a PdRuNi/C tri-metallic nanocatalyst and its excellent catalytic performance for ethylbenzene hydrogenation reaction
Ten Have et al. Using biomass gasification mineral residue as catalyst to produce light olefins from CO, CO2, and H2 mixtures
Yang et al. The structural decoration of Ru catalysts by boron for enhanced propane dehydrogenation
JP4827432B2 (en) Catalyst for FT synthesis reaction
Ma et al. Melamine Modification of the Carrier Regulating the Performance of PtBi/AC in Heptanol Oxidation
Tari et al. Investigating the Long-Term Kinetics of Pd Nanoparticles Prepared from Microemulsions and the Lindlar Catalyst for Selective Hydrogenation of 3-Hexyn-1-ol
Ghosh et al. Role of Nanocatalysis in Chemical Industry